scholarly journals Synthesis of a stable radical anion via the one electron reduction of a 1,1-bis-phosphinosulfide alkene derivative

2008 ◽  
pp. 874-876 ◽  
Author(s):  
Thibault Cantat ◽  
Frédéric Biaso ◽  
Aurélien Momin ◽  
Louis Ricard ◽  
Michel Geoffroy ◽  
...  
Keyword(s):  
Radical Anion ◽  
Stable Radical ◽  
Electron Reduction ◽  
The One

scholarly journals Biomimetic Ketone Reduction by Disulfide Radical Anion

Molecules ◽  
2021 ◽  
Vol 26 (18) ◽  
pp. 5429
Author(s):  
Sebastian Barata-Vallejo ◽  
Konrad Skotnicki ◽  
Carla Ferreri ◽  
Bronislaw Marciniak ◽  
Krzysztof Bobrowski ◽  
...  
Keyword(s):  
Radical Anion ◽  
Radical Mechanism ◽  
Cyclic Ketones ◽  
High Concentration ◽  
Radical Chain ◽  
Ketyl Radical ◽  
Electron Reduction ◽  
The One ◽  
Key Steps ◽  
Radical Chain Reaction

The conversion of ribonucleosides to 2′-deoxyribonucleosides is catalyzed by ribonucleoside reductase enzymes in nature. One of the key steps in this complex radical mechanism is the reduction of the 3′-ketodeoxynucleotide by a pair of cysteine residues, providing the electrons via a disulfide radical anion (RSSR•−) in the active site of the enzyme. In the present study, the bioinspired conversion of ketones to corresponding alcohols was achieved by the intermediacy of disulfide radical anion of cysteine (CysSSCys)•− in water. High concentration of cysteine and pH 10.6 are necessary for high-yielding reactions. The photoinitiated radical chain reaction includes the one-electron reduction of carbonyl moiety by disulfide radical anion, protonation of the resulting ketyl radical anion by water, and H-atom abstraction from CysSH. The (CysSSCys)•− transient species generated by ionizing radiation in aqueous solutions allowed the measurement of kinetic data with ketones by pulse radiolysis. By measuring the rate of the decay of (CysSSCys)•−at λmax = 420 nm at various concentrations of ketones, we found the rate constants of three cyclic ketones to be in the range of 104–105 M−1s−1 at ~22 °C.

The one- and two-electron reduction of 2-thioriboflavin by radical anions of CO2 and dithiothreitol

1986 ◽  
Vol 64 (1) ◽  
pp. 67-70 ◽  
Author(s):  
Parminder S. Surdhar ◽  
David A. Armstrong ◽  
Vincent Massey
Keyword(s):  
Steady State ◽  
Rate Constants ◽  
Radical Anion ◽  
Pulse Radiolysis ◽  
Continuous Production ◽  
Radical Anions ◽  
Reduction Step ◽  
Equivalence Point ◽  
Electron Reduction ◽  
The One

The one- and two-electron reductions of 2-thioriboflavin with[Formula: see text] and cyclic disulphide anion of dithiothreitol [Formula: see text] have been studied by the steady state γ and pulse radiolysis techniques. The [Formula: see text] radical reacted with 2-thioriboflavin to give the neutral semiquinone (•FlH) and the radical anion (•Fl−) at pH 5 and 10 respectively. The pK of the •FlH radical was determined to be 7.4. In the case of the anion, the 2-thioriboflavin spectrum is similar in shape to that of FAD radical anion, but red shifted by 40–50 nm. Red shifts are also seen in the neutral •FlH form for the 370-nm peak and 580-nm shoulder. However, in addition, there is strong enhancement of the absorbance at 500 nm. The spectrum of 2-thioriboflavin semiquinone produced in the presence of 2–5 mM dithiothreitol was perturbed, as was observed previously for unsubstituted flavin semiquinones in the presence of sulphydryls. The rate constants for the initial one-electron reduction step viz: [Formula: see text] were 4.0 ± 0.5 × 109 M−1 s−1 and 1.3 ± 0.2 × 109 M−1 s−1 at pH 7 and 10 respectively. The corresponding rate for the reaction of [Formula: see text] with 2-thioriboflavin at pH 7 was determined to be 2.4 ± 0.2 × 109 M−1 s−l. The continuous production of [Formula: see text] radicals by γ radiolysis reduced 2-thioriboflavin to the dihydro form, and the flavin was regenerated on the addition of air. The[Formula: see text] radical also effected a two-electron reduction. However, in this case, if the process was taken beyond the equivalence point, the dihydroflavin spectrum was bleached and the oxidized flavin could not be recovered.

scholarly journals Redox and Antioxidant Modulation of Circadian Rhythms: Effects of Nitroxyl, N-Acetylcysteine and Glutathione

Molecules ◽  
2021 ◽  
Vol 26 (9) ◽  
pp. 2514
Author(s):  
Santiago Andrés Plano ◽  
Fernando Martín Baidanoff ◽  
Laura Lucía Trebucq ◽  
Sebastián Ángel Suarez ◽  
Fabio Doctorovich ◽  
...  
Keyword(s):  
Soluble Guanylate Cyclase ◽  
Phase Locking ◽  
Cyclic Guanosine Monophosphate ◽  
Guanosine Monophosphate ◽  
Circadian Phase ◽  
Subjective Night ◽  
Circadian Time ◽  
Electron Reduction ◽  
Locomotor Rhythms ◽  
The One

The circadian clock at the hypothalamic suprachiasmatic nucleus (SCN) entrains output rhythms to 24-h light cycles. To entrain by phase-advances, light signaling at the end of subjective night (circadian time 18, CT18) requires free radical nitric oxide (NO•) binding to soluble guanylate cyclase (sGC) heme group, activating the cyclic guanosine monophosphate (cGMP)-dependent protein kinase (PKG). Phase-delays at CT14 seem to be independent of NO•, whose redox-related species were yet to be investigated. Here, the one-electron reduction of NO• nitroxyl was pharmacologically delivered by Angeli’s salt (AS) donor to assess its modulation on phase-resetting of locomotor rhythms in hamsters. Intracerebroventricular AS generated nitroxyl at the SCN, promoting phase-delays at CT14, but potentiated light-induced phase-advances at CT18. Glutathione/glutathione disulfide (GSH/GSSG) couple measured in SCN homogenates showed higher values at CT14 (i.e., more reduced) than at CT18 (oxidized). In addition, administration of antioxidants N-acetylcysteine (NAC) and GSH induced delays per se at CT14 but did not affect light-induced advances at CT18. Thus, the relative of NO• nitroxyl generates phase-delays in a reductive SCN environment, while an oxidative favors photic-advances. These data suggest that circadian phase-locking mechanisms should include redox SCN environment, generating relatives of NO•, as well as coupling with the molecular oscillator.

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